Anthraquinone dyestuffs containing a reactive aliphatic carboxylic acid group



tates 3,076,610 Patented Dec. 25, 1962 ice This invention provides water-soluble anthraquinone dyestufis of the formula -soin (in which one of the two X is a hydrogen atom and the other X a chlorine atom) and advantageously radicals containing labile halogen atoms. In such radicals the labile halogen atom, that is to say, one capable of reacting with fibrous materials, may be bound to a heterocyclic radical containing two nitrogen atoms, for example, to a pyramidine radical or to the acyl group of an acid containing at least one acid group of the constitution for example an acyl group derived from barbituric acid, cyanuric acid or an aliphatic carboxylic acid. When the acyl group is that of cyanuric acid, the dyestuff contains at least ,one halogen atom bound to a 1:3:5-triazine ring. for example, a dichlorotriazine radical or a monochlorotriazinefradical, such as the radical of the formula C--Cl l I] in which X represents an amino group which may be substituted or a substituted hydroxyl group. The acyl groups containing halogen and derived from aliphatic carboxylic acids advantageously contain only a few carbon atoms, for example, 23 carbon atoms. As examples there may be mentioned the chloracetyl radical, the m or ,B-chloropropionyl radical and above all the oz-fi-dichloropropionyl radical.

The invention also provides a process for the manufacture of the dyestuffs of the above Formula 1, wherein an anthraquinone dyestutf of the formula Cnd fln-l nr-I Zm-I in which Z, R, X, R n and m have the meanings given above, and B represents an acylatable amino group, advantageously a free amino group, is reacted With an an-- hydride or halide of an acid of which the acyl group is capable of entering into chemical combination with the fibrous material, so that the acylatable amino group B is acylated.

As anhydrides 0r halides of acids of which the acyl group is reactive there may be mentioned, for example, the anhydrides and halides of aliphatic cup-unsaturated carboxylic acids, for example, chloromaleic anhydride, propiolic acid chloride, acrylic acid chloride and especially the halides of aliphatic carboxylic acids containing labile halogen atoms, such as chloracetyl chloride, sulfochloracetic chloride, B-bromoor B-chloro-propionic acid chloride, ot-B-dichloropropionic acid chloride, and also tri-chloropyrimidine and preferably cyanuric chloride or a primary condensation product of cyanuric chloride which contains two chlorine atoms and, instead of the third chlorine atom, a free amino group or an organic radical. Such primary condensation products can be obtained by methods in themselves known from one molecular proportion of cyanuric chloride and one molecular proportion of a reactive organic hydroxyl-compound (for example, one molecular proportion of a phenol or alcohol), and one molecular proportion of ammonia or of an organic amine, such as methyl-amine, isopropylamine, cyclohexylamine or phenylamine, dimethyl-amine, N-ethylphenylamine, -methoxy-propylamine, phenyl-hydrazine sulfonic acids, aminoethane sulfonic acid, amino-acetic acid, ortho-, metaor para-aminobenzoic acid, amino-benzene sulfonic acid, such as ortho-, metaor para-amino-benzene sulfonic acid and l-aminobenzene-Z:S-disulfonic acid, aminophthalene sulfonic acids, and also mercapto-acetic acid or the like.

The starting materials of the Formula 2 can be prepared by the usual methods, for example, by condensing an aminoanthraquinone of the formula Halogen in which the symbol Z has the meaning given in connection with Formula 1, with an aminobenzene sulfonic acidc amide or carboxylic acid amide of which the amide radical contains an acylatable amino group or an acylated amino group of which the acyl group may, be split off by hydrolysis, if desired, after the condensation.

As aminobenzene sulfonic acid amides and 'icarboxylic acid amides which are to be condensed with the 4-halogen-, especially 4-bromo-l-aminoanthraquinone-Z:5- or -2:6 01'. -2:7- or -2:8-disulfonic acid, or more especially with the 4-bromo-1-aminoanthraquinone-Zsulfonic acid, there may be mentioned: 1-aminobenzene-3- or -4-carboxylic acid- N-(4'-aminophenyl)-amide-3'-sulfonic acid, l-aminobenzene-3- or -4-sulfonic acid-N-(5'-amino-2'-methylphenyl)- amide-4'-sulfonic acid, l-aminobenzene-3- or -4-carboxylic acid-N(3-arninophenyl)-amide-4-sulfonic acid, l-aminobenzene-3- or -4-sulfonic acid-N-(3'-aminophenyl)-amide- 4-sulfonic acid, l-aminobenzene-3- or -4-sulfonic acid- N-(4'-aminophenyl)-amide-3-sulfonic acid, 4-methylor 4-chloro-l-aminobenzene 3 sulfonic acidN-(3'-aminophenyl)-amide-4'-sulfonic acid, and also l-aminobenzene- 3-sulfonic acid-N-(5'- or -4-acetylaminophenyl)-arnide- 2'-sulf0nic acid, 1-aminobenzene-3- or -4-sulfonic acid-N- (3'-acetaminophenyl)-amide 4' sulfonic acid, l-aminobenzene-3- or -4-sulfonic acid-N-(B-acetaminoethyl)- amide, the corresponding acetylamino-hexylamide and l-aminobenzene-S- or -4-sulfonic acid-N-(3'-acetaminophenyl)-amide, of which the acetyl amino group is hydrolsyed after the condensation with a 4-halogen-l-aminoanthraquinone.

The condensation or acylation of the dyestuffs of the Formula 2 obtainable from the above compounds is advantageously carried out in the presence of an acid-binding agent, such as sodium acetate, sodium hydroxide or sodium carbonate, and under conditions such that the resulting product contains a reactive substituent, more especially a reactive halogen atom. Thus, the acylation may be carried out, for example, in an organic solvent or at a relatively low temperature in an aqueous medium. When cyanuric chloride is used as acylating agent the dyestuff formed by the primary condensation and having the formula in which Z, R, X, R in and n have the meanings given in connection with Formula 1, and Y represents a 2:4-dichloro-l :3:5-triazine ring bound in the 6-position through an amino bridge to R is reacted with ammonia, an alcohol or a phenol or more especially with an organic monamine to form a secondary condensation product, the reaction being advantageously carried out at a somewhat raised temperature, for example, within the range of 30 C. to 90 C., and advantageously 40 C. to 60 C., whereby the condensation proceeds more rapidly and completely than at lower temperatures, and it is surprising that the third chlorine atom of the cyanuric chloride is not attacked.

The dyestuffs of the Formula 1 are new. They are valuable dyestufis for dyeing or printing a very wide variety of materials, especially nitrogenous fibers such as wool, superpolyamides, leather, silk, and also polyhydroxylated materials of fibrous structure, such as cellulosic materials including synthetic fibers, for example of regenerated cellulose, and natural materials, for example, linen, cellulose or above all cotton. They are suitable for dyeing polyhydroxylated fibrous materials by the so-called direct dyeing methods and also by the pad-dyeing method, especially from an alkaline aqueous solution, which may contain a high concentration of salt, for example, by the process in which the dyestuff is fixed on the material by means of an acid-binding agent at a raised temperature. The dyeing of nitrogenous fibers, such as wool, is advantageously carried out from an acid to neutral bath, if desired, in the presence of a compound containing at least one basic nitrogen atom, to'which is bound at least one radical contain- A ing a polyglycol ether chain, the molecule containing at least four groups (advantageously CH --CH O-- groups) and at least four carbon atoms not forming part of such groups, for example, in the presence of a nitrogen compound of the formula Example 1 38.2 parts of 1-amino-4-bromanthraquinone-Z-sulfonic acid and 44.0 parts of 4-aminotoluene-Z-sulfonic acid-N- (3'-acetyl-aminophenyl)-amide-4'-sulfonic acid are pasted in 400 parts of water and mixed with 60 parts of sodium bicarbonate. 1 part of cuprous chloride is added and the mixture is heated to and stirred at to C. until brornamino-anthraquinone-sulfonic acid can no longer be detected. The blue dyestufi of the formula (I? NH:

SOaH

NHGCH:

NHCOCH:

-SOsH is separated by acidification and salting out, filtered off and, if desired, washed with sodium chloride solution.

To hydrolyse the acetyl group and liberate the amino group, the resulting dyestuff paste is stirred in 200 parts of water, heated to 80 C. and refluxed for several hours with 400 parts of a sulfuric acid solution of tic-naphthalenesulfonic acid containing 30% by weight of rat-naphthalenesulfonic acid. On cooling, the hydrolysed dyestuff precipitates in crystalline form.

parts of ice are added to a solution of 19 parts of cyanuric chloride in 80 parts of acetone. The resulting suspension of cyanuric chloride is run into a neutralised solution, cooled to +2 C., of 65.8 parts of the dyestufi of the formula El) N111 O NH- CH: NH:

6 in 1500 parts of water. By gradual addition of 50 parts and by volume of 2 N-sodium hydroxide solution the reaction mixture is maintained constant at pH=6 to 7. After stirring for about 2 hours the condensation is complete.

A solution of 17.3 parts of 1-aminobenzene-3-su1fonic 5 I COCHa acid in 500 parts of water is added, and the reaction mixture is slowly raised to a temperature of 30 to 50 C.,

and the liberated acid is again continually neutralised 303E with a total of 50 parts by-volume of 2 N-sodium hydroxide solution. On completion of the reaction the 10 can likewise b prepared in analogous manner by using resulting dyesiufi i5 salted out With Sodium Chloride, instead of para-nitrotoluene-ortho-sulfonyl chloride corfiltered Off and dri d; it f rms a blue powder which disresponding proportions of 5-nitro-2-chlorophenyl-l-sullv s in w r wi h l l r n and in n n r e fonyl chloride or of meta-nitrobenzenesulfonyl chloride. sulfuric acid with green-blue coloration and dyes cotton Exam le 2 and regenerated cellulose by the process described in Exp ample 6 full, reddish blue tints of good fastness to wash- When in Example 1, paragraphs 1 to 3, instead of 4- ing and light. amino-l-methylbenzene-Z-sulfonic acid N (3 acetyl- Prior to the condensation with 1-aminobenzene-3-sulaminophenyl)-amide-4-sulfonic acid, 40 parts of 4-aminofonic acid, the corresponding dichloro-dyestuff can be iso- 1-methylbenzene-Z-sulfonic acid-N-(3' aminophenyl)- lated in powder form by addition of salt, filtration and amide-4-sulfonic acid are condensed with 38.2 parts of drying; it dyes wool and cotton blue tints. 1-amino-4-bromanthraquinone-Z-sulfonic acid to 60 to When wool is dyed with this dyestuif from a weakly 70 C. instead of at SO-90 C., and the reaction mixture acetic acid bath, valuable blue tints of good fastness is further worked up, a dyestutf is obtained which has properties are likewise obtained. identical properties.

The 4-amino-1-methylbenzene-2-sulfonic acid-N-(3'- Example 3 (N) NH:

/O\ S0 H I r it 3 0 NH- NH-C G-NH G SORNH SOSH 1103's acetyl-aminophenyl)-amide-4'-sulfonic acid used in this 100 parts of ice are added to a solution of 19 parts example can be prepared, for example, as follows: 40 of cyanuric chloride in 80 parts of acetone. The re- 23.5 parts of para-nitrotoluene-ortho-sulfonyl chloride sulting suspension of cyanuric chloride is mixed with a and 19.0 parts of 2:4-diaminobenzenesulfonic acid are solution, cooled to 0 C., of 32.7 parts of the disodium pasted in 500 parts of water and at a slightly raised temsalt of 1-aminobenzene-2:S-disulfonic acid in 330 parts perature the reaction mixture is kept weakly alkaline by of water. In the course of 2 hours 55 parts by volume of addition of 10 parts of sodium hydroxide solution of 30% 2 N-sodium carbonate solution are added dropwise, while strength. On completion Of the condensation the sulfonmaintaining the temperature at 2 t0 4 C, by external amide iormedis quantitatively Precipitated y acidification cooling. A clear solution is obtained of the condensa- Wiih hydrochloric acid, filtered Off if desired, Washedtion product from equimolecular proportions of cyanuric The Crude crystalline H1385 is then dissolved in 100 chloride and l-aminobenzene-Z:S-disulfonic acid which,

parts of Water y adding 10 Parts O Sodium hydfoxide if desired, can then be purified by being filtered. Solution of 30% Sirengih- Paris of aceiafihydrlde f 50 The resulting solution is added to an aqueous neutral added, whereupon acetylation sets in spontaneously with l i h d t 40 (3,, f 643 parts f th d e t fi evolution of heat, and the acetyl derivative precipitates of the f r ula in magnificent crystals. 0 NH,

The reduction of the nitro group is carried out in the H conventional manner by Bchamps method with iron SO3E and hydrochloric acid. When the reduction mixture is alkalinised, purified by filtration, acidified and treated with sodium chloride, the 4-amino-Lmethylbenzene-Z- sulfonic acid-N-(3-acetylaminophenyl)-amide-4'-sulfonic 5 NH NH, acid is obtained in crystalline form.

When the 2:4-diaminobenzene sulfonic acid is replaced SOZNH by 23 parts of 4-acetylamino-Z-aminobenzenesulfonic acid, proceeding otherwise in identical manner, 4-amino- B038 1 methyl benzene 2 sulfonic acid N (5 acylaminophenyl)-amide-2'-sulfonic acid is obtained.

The compounds of the formula in 1500 parts of water, and the pH value of the reaction mixture is maintained constant at pH=6 to 7 by the gradual addition of 50 parts by volume of 2 N-sodium' hydroxide solution. On completion of the condensation the dyestuff is salted out with sodium chloride, filtered off and dried in a vacuum cabinet at 70 to C. It forms a blue powder which dissolves in Water with blue NHCOCH! coloration and dyes cotton by the method described in Example 6 reddish blue tints which are fast to washing C1 303E and 7 By the method described above further dyestuffs which dye reddish blue tints are obtained by condensing cyanuric chloride or cyanuric bromide with the anthraquinone with the compounds in Column 11 dyestuffs shown in Column I of the following table and IIQHa o o 1.--. [I 403R NH -SOZNH -NH2 SOaH IFH: o o 2 g 503B 0 0 NH 402m: NH:

som

IIIHI CO\ a.. sea

NH SOqNH NH2 0 0 4-..- 0 -SO;H oo

NH 0 0-NH NH:

SOsH

00 5...- -som NH SOT-NH NH:

HOaS

0 0 6..-- 0 soul 0 0 NH SOrNH NH:

C0 7.-.- Oi sons: 00

NH SOr-NH NH2 l-aminobcnzene 3-sulfoulc acid.

l-aminobenzeuc- 2-sulfomc 861d.

l-aminobcnzeued earboxylic acid-fi-sultonic acid.

1-aminobenzene- 2-carboxyhc acid-4-sulfonic acid.

Example 6 reddish blue tints which are fast to washing and light.

Further dyestuffs which produce similar tints are obtained by this method when the anthraquinone dyestulfs shown in Column I of the following table are condensed in an analogous manner with the compounds in C01- umn H.

co 1103s SOsH (ll-(l) SOaH prolonged period with 250 parts of a sulfuric acid solution of about 15% strength of a-naphthalenesulfonic acid for the purpose of the hydrolysis of the acetylamino group. Filtration of the reaction mixture yields the dyestufl of the formula S OaNH-CHa-GHg-NH:

or its sulfate respectively.

51.6 parts of this dyestuif in 1500 parts of water are neutralised with sodium hydroxide. The neutral solution is treated with an aqueous solution (prepared from 19 parts of cyanuric chloride and 32.7 parts of the disodium salt of 1-aminobenzene-2:S-disulfonic acid) of the primary condensation product which, in the form of the free acid, corresponds to the formula Cl SOaH The pH value of the reaction mixture is kept constant at 6 to 7 by gradually adding a 2 N-aqueous solution of sodium hydroxide. On completion of the condensation the dyestuff is salted out with sodium chloride, filtered off and dried in a vacuum cabinet at 70 to 80 C. It forms a blue powder which dissolves in water with blue coloration and dyes cotton by the method described in Example 5 13.16 parts of the dyestutf of the formula 00 SOaH sozNH in 1500 parts of water are neutralised with sodium hydroxide and 13 parts of anhydrous sodium acetate are added. While stirring vigorously, 7.23 parts of acrylic acid chloride in 50 parts of acetone are added dropwise at 0-5 C. in the course of 15 minutes. After /2 hour the solution is adjusted with sodium carbonate to pH=9, and the dyestuft is salted out with 200 parts of potassium chloride and filtered off. The dyestufi dyes wool and cotton reddish blue tints.

Similar dyestuffs are obtained when the acrylic acid chloride is replaced by 10 parts of a-chloracrylic acid chloride or B-chloropropionic acid chloride and the liberated hydrochloric acid is neutralised with sodium carbonate or sodium bicarbonate.

When 13.16 parts of the dyestuif of the formula SOaH SIOQNH are used and the acylation is performed as described above The resulting filaments are stretched by 25% and colwith chloracetyl chloride or with azfi-dichloropropionic lected in a spinning can rotating at 6000 revolutions per acid chloride, the resulting dyestufi likewise gives reddish minute. blue tints. The cake obtained in this manner is after-treated in a A similar dyestutf is obtained by this method from closed apparatus with circulating liquor; it is first rinsed fl-chloro-propionyl chloride and the 1-amino-4-pheny1- for minutes with water heated at 60 to 70 C., then amino anthraquinone-3'-sulf0nic acid-N-(B-aminoethyD- desulfurised for 20 minutes at 70 C., with a solution amide-Z-sulfonic acid mentioned in Example 4. containing per liter 5 grams of sodium sulfite, then again Example 6 rinsed, and finally brightened for 10 minutes at 50 C. with a solution of 50 grams of sodium oleate per liter. 1 P of the dyestufi Obtained as described in Example The cake is then freed from its water content and dried. 3 is dissolved in 100 parts of Water. A fabric of regener- A bl dyeing i bt in d hi h i f t t hi ated cellulose staple fiber is impregnated with the result- Wh t i l i d i ing solution until the fabric shows an increase in weight 1, A water-soluble anthraquinone dye t fi f h f of 75% and then dried. The fabric is then impregnated la with a solution of C. containing per liter 10 grams of NH:

sodium hydroxide and 300 grams of sodium chloride,

squeezed to a weight increase of 75%, the dyeing is steamed for 60 seconds at 100 to 101 C., rinsed, treated Z in a sodium bicarbonate solution of 0.5% strength, rinsed, 20

soaped for 15 minutes in a boiling solution of a non-ionic 00 SOrNH-R NH-Y detergent of 0.3% strength, rinsed and dried. A reddish NH blue dyeing results.

00 -so3rr Example 7 I A dyebath is prepared from 4000 parts of water, 5 parts 5 R of acetic acid of strength, 10 parts of crystalline sodium sulfate, 1 part of the addition product described in which Y represents the acyl radical of an acid selected below or octadecenylamine and ethylene oxide and 2 parts from the group consisting of acrylic acid, a-chloroacrylic of the dyestutf of the formula acid, chloracetic acid, ,B-chloropropionic acid, and cali- SOaH C1 S0 H I? f, a i l IH NH-C C-NH SOaNH SOsH At 60 C., 100 parts of woolen piece goods are immersed dichloropropionic acid, Z is selected from the group conin this dyebath which is then raised to the boil within half sisting of -SO H and hydrogen, R is selected from the an hour, and dyeing at the boil is performed for 1 hour. group consisting of hydrogen and lower alkyl, and R is The wool is then withdrawn from the dyebathif desired, a divalent radical selected from the class consisting of after addition of 0.8 part of an aqueous ammonia solution benzene radical and ethylene radical.

of 25% strength-immediately rinsed in water and dried. 2. The water-soluble anthraquinone dyestuff of the A level reddish blue dyeing is obtained which has good formula fastness to light and wetting.

The ethylene oxide addition product is prepared in the following manner:

100 parts of commercial octadecenylamine are mixed SO8H with 1 part of finely disintegrated sodium, the whole is heated to 140 C. and ethylene oxide is introduced at 135 to 140 C. When the ethylene oxide is being con- I SO2NH NH-OOC=CH:

sumed rapidly, the reaction temperature is lowered to 120125 C., and the introduction of ethylene oxide is continued until 113 parts thereof have been absorbed. HO3S The resulting reaction product gives an almost clear solution in water.

Example 8 1 part of the monochloro-triazine dyestuif obtained as The anthlaquinone dyestllfi 0f the formula described in Example 1 is dissolved in 50 parts of water and stirred into 1175 parts of a viscose xanthate solution of 8.5% strength, corresponding to a content of parts of a-cellnlose. The mass is stirred for /2 hour and then 00 stored for 60 hours at room temperature.

The viscose mass is then spun through spinnerets, in the 7 manner conventionally employed for the manufacture of 0 viscose rayon yarn, and coagulated at 45 C. in a precipitation bath containing per liter grams of sulfonic acid of 96% strength, 270 grams of sodium sulfate and 10 grams of zinc sulfate. 75

soan NH S OaNH-OHzCHr-NH-CO-CHz-Cl 15 16 4. The anthraquinone dyestuff of the formula 6. The water-soluble anthraquinone dyestuff of the formula S0 11 NH,

/CO so H 00 3 NH- s OnNH -NH-C OCHC H:

Cl 01 CO CH; SO H NH SOq-NH- NHC O-CHy-CHzCl 5. The water-soluble anthraquinone dyestufi of the for- Ho s mula /C0 so H References Cited in the file of this patent UNITED STATES PATENTS CO 2,453,104 Vogt Nov. 2, 1948 2,659,736 Von Allmen et a1. Nov. 17, 1953 NH SOT-NH NH-c 04 1:0111 2,670,356 Weinand Feb. 23, 1954 Hess FOREIGN PATENTS 534,107 Balgium -2 June 14, 1955 

1. A WATER-SOLUBLE ANTHRAQUINONE DYESTUFF OF THE FORMULA 